Hair setting composition comprising an aqueous dispersion of a tertiary aminoalkyl ether of starch



United States Patent M HAIR SETTING COMPOSHTION COMPRISING AN AQUEOUS DISPERSION OF A TERTIARY AMil lG- ALKYL ETHER 0F STARCH Martin M. Rieger, West Englewood, N..l., and George Berenbom, Brooklyn, N.Y., assignors to Warner- Lambert Pharmaceultieal Company, Morris Plains, Null, a co oration of De aware No nawing. Filed July 16, 1962, Ser. No. 210,231

9 Claims. (Cl. 16787.1)

This invention relates to novel hair setting compositions containing a film-forming etherified starch and relates to a novel process for the production of such compositions.

An object of this invention is to provide an efiic1ent and effective method for hair setting using the novel composition of this invention. Other objects of this invention will appear from the following detailed description.

The permanent waving of human hair involves treating the hair to render it somewhat plastic and non-resilient, altering the original shape of the hair and thereafter fixing it in the new shape. Thus, for example, in cold permanent waving processes the hair is first softened by application of a waving solution. An aqueous solution of the ammonium salt of thioglycolic acid has been found to be suitable for this purpose. This substance acts as a chemical reducing agent and softens the hair by breaking certain of the disulfide bonds which are present in the hair structure. By this treatment the natural resiliency of the hair is reduced and, by winding it on curlers and the like, its shape and configuration may be readily altered. The subsequent application of an oxidizing agent, such as hydrogen peroxide or an alkali metal perborate, for example, to the softened hair structure while it is still in the shape imparted to it by being wound on curlers, acts to restore a major part of the original resiliency to the hair by recreating some of the broken chemical bonds thereby causing the hair to assume the new and desired configuration.

Such chemical treatments of hair are expensive and cumbersome and may produce brittle hair ends and irritation of the scalp. Plain water, on the other hand, will also soften the hair somewhat so that it is possible to alter the original shape of the hair and to impart a curl. This method, although cheap, safe and widely available, does I not give any permanence to the altered configuration because, after the water evaporates, the normal resilience of the hair, particularly if it tends to be straight, Will cause it to uncurl and return to its original shape and form. This change takes place quickly under the influence of humidity as well as from the usual disturbance to the hair-set which is experienced in ordinary daily wear.

Prior to our discovery, many film-forming agents have been proposed for use in hair setting compositions. For example, a colloidal solution containing a gum such as tragacanth or a resin such as shellac may be applied to the hair after setting in the desired configuration, and, upon drying the hair, the residual film of material retains the set. The films formed of these materials are, how ever, quite brittle, and the film holding th setting is easily broken if the hair is disturbed. This not only reduces the hair holding power of the material but also leads to an undesirable condition known as flaking. Moreover, some of these film-forming agents, especially some of the resins, are water insoluble and are not easily removed.

It is a principal object of this invention to provide a novel hair-setting composition which can be used conveniently, yet can be removed easily, and which possesses to an enhanced degree the desirable hair-setting properties of other prior art substances.

lidfiflli Patented June 1, 1965 It has now been found that hair may be set and thereafter held in the desired configuration if an aqueous solution of a tertiary aminoalkyl ether of an amylaceous material such as etherified corn starch is applied to clean, dampened hair; the treated hair is placed in curlers and, after the hair has dried, the dry film formed from the solution of etherified corn starch is allowed to remain and to hold the setting after the curlers have been removed. The film thus left on the hair has also been found to impart to the hair a desirable silky finish which is both soft and flexible. By this treatment the hair will retain the shape in which it has been curled for a considerable period or" time and will lose its shape only when the hair is shampooed or is rinsed with water whereby the setting agent is removed. Thus, the hair setting is essentialy permanent, although it can easily be removed when desired. This semi-permanent hair setting composition and the method of hair styling involved in its use is outstanding because of its ease in application and the durable efiect which may be achieved. The ease of removal of the composition which produces the hair setting is also an added factor, and the total effect achieved constitutes a significant advance in the art of hair styling and setting, particularly in view of the fact that modern beauty trends are toward a more frequent alteration of hair styling and setting which is accomplished either at home or at the beauticians.

Furthermore, when the novel hair-setting composition we employ is applied to the hair, the film that forms upon drying will not only adhere tenaciously to the hair without flaking but will also resist any environmental changes, such as high humidity. Thus, for example, when the dried film is exposed to a relative humidity of for 24 hours, the film does not become at all tacky. In contrast, the films formed from hair-setting compositions such as gums or polyvinyl-pyrrolidones become quite tacky at 90% humidity. Such tackiness is quite objectionable in hair to which a setting composition has been applied not only because of the discomfort which results but also because of the dust and dirt which are readily attached to the hair by a tacky film. The tertiary amino alkyl ethers of amylaceous materials useful in forming the novel compositions of this invention must be of a chemical structure which meets certain critical factors essential to the successful formulation of these novel hair-setting compositions.

The ethers yielding the most desirable results when employed in the compositions of our invention have the general formula R2 R is an alkyiene or hydroxyalkylene radical and R and R are alkyl, aryl or aralkyl radicals. These compounds and their chemistry are generally described in US. Patent 2,813,693.

These modified materials may be produced, for example, by reacting ungelatinized starch with an etherifying agent containing a tertiary amino radical, such as, for example, a dialkyl amino ethyl chloride employing an alkaline reaction medium. This reaction adds a positive electrical charge to the etherified and quaternized starch molecule, and the positively charged molecule thus formed has a marked atfinity for negatively charged material such as human hair. The electrical afiinity between the positively charged starch and the negatively charged hair causes the modified starch to adhere strongly to the hair. To produce the necessary electrical balance for optimum adherence of the starch to the hair, the amount of the tertiary amine group introduced is precisely controlled, since this wherein X is starch,

is the group which contributes the positive electrical charge to the altered molecule. A total nitrogen content of from 0.25% to about 2% nitrogen as determined by the Kjeldahl method imparts an optimum aflinity for hair to these starch ethers.

Starch such as that derived from maize, potato or corn exists in the form of discrete granules and contains both amylose and amylopectin among its constituents. The unique properties of amylose and amylopectin have been found to be responsible for the desirable hair-setting properties of these compositions. Under the influence of heat or of certain chemicals such as alkali metal hydroxides, and in the presence of water, the starch granules will swell and on disruption will release these constituents. Both of these constituents are 'dispersible in water and form a gelatinous colloidal dispersion. When this dispersion is applied to the hair the .amylose and amylopectin are retained by the hair in the form of a thin film after the water evaporates. It is this film which holds the hair in the altered confguration in which it has been set by Winding on rollers and the like. Hair, after being set by the application of this novel composition, retains the shape of the set even when disturbed, since the film is not only flexible but adheres strongly to the hair. The amylose content contributes the desirable film-forming properties to the composition, whilst the amylopectin present acts to hold the amylose film together. Films formed of amylose alone are quite flexible. When amylopectin is present so that it is able to hold the film together, the resulting films resist cracking and also adhere strongly to the hair. The ratio of amylose to amylopectin which is present in the starch is quite critical in obtaining the desired result. Thus, for example, in order to obtain optimum hair setting qualities, the starch should contain the amylose and amylopectin in the proportions of from to 50 parts by weight of amylose to 75 to 50 parts by Weight of amylopectin. When the ratio of these components is in the proportions indicated, the modified starch is found to have optimum film-forming and adhesive properties. The absence of amylose, for example, results in complete loss of hair-setting properties. The compositions of this invention are prepared by dispersing in cold water etherified and quaternized starch having 0.25 to 2% Kjeldahl nitrogen and an amyloseamylopectin ratio as indicated and then heating the dispersion to a temperature of 75 to 85 C. for from 25 to minutes. This treatment produces a gelatinous dispersion in which the original starch granules no longer exist. This dispersion is ready for use after rapid cooling to 25 to 27 C.

It has also been found that the heating time is quite critical as well. If the heating time is reduced below 20 minutes at the temperatures indicated, the amylose is not sufiiciently solubilized, whereas if the heating extends be yond minutes, a paste of solubilized amylopectin results.

While an ordinary aqueous dispersion as described is satisfactory for use as such, a more desirable and cosmetically acceptable composition is obtained if other ingredients are added. Thus, the composition may also include varying amounts of perfume, hair conditioning agents such as the stearyl ester of cholaminoformylmethyl pyridinium chloride or stearyl dimethyl benzyl ammonium chloride, lower aliphatic alcohols, plasticizers such as urea, or one or more humectants, such as glycerin, sorbitol, propylene glycol and the like.

The following examples are given in order further to illustrate this invention.

Example I 1.5 parts by weight of etherified cornstarch as disclosed in U.S. Patent No. 2,813,093 and containing 28% amylose, 72% amylopectin and 0.25% nitrogen, a product available commercially under the designation Cato Starch)? is dispersed in 2.5 parts by Weight of Water at a temperature utes. 46 parts by Weight of water at a temperature of 15 to 20 C. are then added to the gelatinous solution. The solution obtained is cooled rapidly to a temperature of 25 to 27 C. and is then ready for use in forming hairsetting compositions. The starch solution thus obtained will be referred to hereinafter as Composition A. This composition may be employed as such or may be formulated together with other added ingredients, as described below in Examples 2 to 7, by being combined with humectants, plasticizers and the like.

In order to obtain suitable aqueous hair-setting compositions, the following ingredients are combined by simple blending procedures in the proportions given:

Example ll Parts by weight Glycerol (105-20 Stearylester of cholamino formylmethyl pyridinium chloride (Witco Chem. Co.) 0.025-05 Alcohol (SDA #40) 030.0 Perfume 0.5 Formaldehyde solution 0.5 Composition A, q.s. to 100.

Example III Parts by weight Stearyl dimethyl benzyl ammonium chloride (Rohm & Haas) 1.04.0 Alcohol (SDA #40) 020.0 Perfume 0.5 Formaldehyde solution 0.5 Composition A, q.s. to 100.

Example IV Parts by weight Ethoxylated lanolin (Robinson-Wagner) 0.5-2.0 Perfume 0.5 Formaldehyde solution 0.5 Composition A, q.s. to 100.

Example V Parts by weight Cationic long chain fatty amine (Atlas Chem.

Ind.) 1.0-4.0 Perfume 0.5 Formaldehyde solution 0.5

. Composition A, q.s. to 100.

Example VI I Parts by weight Urea 0.5-4.0 Perfume 0.5 Formaldehyde solution 0.5 Composition A, q.s. to 100.

Example VII 7 Parts by weight 'Stearylester of cholamino formyl methyl pyridinium chloride (Witco Chem. Co.) 0.5-1.5 Avitex Q (Du Pont) (long chain quaternary amine softener) 2.0-5.0 Stearyl alcohol (melted) 1.5-5.0 Perfume 0.25-0.75 Composition A, q.s. to 100.

It is understood that the foregoing detailed description is given merely by way of illustration and that many variations may be made therein without departing from the spirit of our invention. a a i Having described our invention, what we desire to se- 4 of 15 to 20 C. An additional 50 parts'by weight of Water are then added and the resulting dispersion heated at a temperature of to C. for from 25 to 30 mincure by Letters Patent is:

1. A hair-setting composition comprising about 1 to 2 percent by weight of an aqueous dispersion of a tertiary aminoalkyl ether of starch of the formula wherein X is starch, R is a member selected from the group consisting of alkylene and hydroxyalkylene and R and R each is a member selected from the group consisting of alkyl, aryl and aralkyl, said starch containing by Weight 0.2% to 2% nitrogen and amylose and amylopectin in the proportions of from 25 to 50 parts by weight of amylose to 75 to 50 parts by weight of amylopectin.

2. A method for setting hair which comprises applying to the hair an aqueous starch dispersion obtained in accordance with claim 1, shaping the hair to the desired configuration and allowing the water to evaporate.

3. A hair-setting composition as defined in claim 1 wherein said hair setting composition contains in combination therewith about 0.025 percent to about 5 percent by weight of a hair conditioning agent selected from the group consisting of the stearylester of cholamino forrnyl methyl pyridium chloride, stearyldimethyl benzyl ammonium chloride, and ethoxylated lanolin.

4. A hair-setting composition as defined in claim 1 wherein said hair setting composition contains in combination therewith 0.05 to 2.0 percent by Weight of a humectant selected from the group consisting of glycerol, sorbital and propylene glycol.

5. A hair-setting composition as defined in claim 1 wherein said hair setting composition contains in combination therewith 0.5 to 4.0 percent by Weight of urea.

6. A hair-setting composition as defined in claim 1 wherein said hair setting composition contains in combination therewith about 0.5 percent by weight of formaldehyde.

7. A hair-setting composition comprising the combination of a 1 to 2 percent by weight of an aqueous dispersion of a tertiary amino alltyl ether of starch of the formula said starch containing by weight about 0.25% nitrogen, and amylose and amylopectin in the proportions of about 28 parts by weight of amylose to about 72 parts by weight of amylopectin with about 0.025 to 0.5 percent by weight of the stearyl ester of cholamino formyl pyridinium chloride, about 1 to 30 percent by weight of alcohol and about 0.5 percent by weight of formaldehyde.

6 8. A hair-setting composition comprising the combination of a 1 to 2 percent by weight of an aqueous dispersion of a tertiary amino alkyl ether of starch of the formula Starch-O- Cal-LN 2 5) 2 said starch containing by weight about 0.25% nitrogen, and amylose and amylopectin in the proportions of about 28 parts by weight of amylose to about 72 parts by weight of amylopectin with about 0.025 to 0.5 percent by weight of urea and formaldehyde.

References Cited by the Examiner UNITED STATES PATENTS 2,655,923 10/53 Gallenkarnp 16787.2 X 2,793,930 5/57 Mamlok 167-87.2 X 2,813,093 11/57 Caldwell et al 260-233.3 2,854,449 9/58 Monson et a1 260 233.3 2,928,772 3/60 Anderson 16787 OTHER REFERENCES Botwright: Journal of Society of Cosmetic Chemistry, vol. 3; pages 118-123 (1952).

General Aniline and Film Corp. (GAP), 747,806, Apr. 11, 1956 (British) (5 pages specification).

Sagarin: Cosmetics, Science and Technology, Interscience Publishing Inc., New York (1957), pages 135, 162-463, and 533-534.

Wagner: American Perfumer, (7): pages 23-26, July 1960.

JULIAN S. LEVITT, Primary Examiner. LEWIS GOTTS, Examiner. 

1. A HAIR-SETTING COMPOSITION COMPRISING ABOUT 1 TO 2 PERCENT BY WEIGHT OF AN AQUEOUS DISPERSION OF A TERTIARY AMINOALKYL ETHER OF STARCH OF THE FORMULA 